TW200418796A - Process for the preparation of stabilizers for polymers - Google Patents

Abstract

The instant invention relates to a process for the preparation of stabilizers for polymers, especially for polyamides, by condensation of isophthalic acic dichloride (IPC) with sterically hindered amines of the type tetraalkylpiperidine. By using organic solvents or mixtures of organic solvents with water and by an optimized combination of temperature and pressure the yield is much higher than by using water alone. The organic load of the waste water could be significantly reduced.

Description

200418796 (1) (ii) Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for preparing a polymer, especially a polyamine. [Previous technology] The life of polyamines is determined by the additives used in the manufacturing process to stabilize polymers against melt processing and environmental climatic factors. One point in providing stabilization systems for polyamides is the fact that the maximum concentration of many additives is limited. Poly believes that it is poor in solubilizing additives, especially for non-polar additives with relatively low molecular weight relative to amine polymers. Manufacturers of face-based polymer-based molded and extruded articles are striving to include low concentrations of additives. Stabilizers or stabilizer systems for stabilizing polyamidamine have been mentioned, for example, among the following: US 4,003,875 (asymmetric one brewer fee) 'US 5,045,083 (copper complex and straw UV absorption Agent), US 4,5 44,69 1 (graspidate, benzoic acid, α-cyanocinnamic acid vinegar and o-hydroxyphenylbenzotrisine) US 5,338,319 (copper complex and diaryl oxalate Amines) or US 5,3 8 0,7 7 4 (phenolic antioxidants, phosphites, amines and benzotriazoles of choice). Polyamine polymers are characterized by high tensile strength, Anti-abrasion polyamines also need stabilizers to resist thermal oxidative degradation and photodegradation stabilizers. The severe lack of amines caused by polyamines is used by the other parties in order to pass some warp-type oxalates to aniline malonates.) Stabilizer properties Do not continue to maintain these properties in long-term applications such as Pe-4200418796.

Jit exopolyamide must undergo a lightfast dyeing system. Discoloration of the matrix is considered to be highly critical and may cause hue changes in colored objects, such as polyamide polymer fibers and molded articles. Therefore, it is always necessary to further improve the stabilization system of polyamide polymers. The most powerful stabilizer for polyamide stabilization mentioned in WO 9 7/4 3 3 3 5 for the first time can be represented by the general formula (1) See (see below for definition of basis)

This powerful stabilizer can be added to the polyamide melt to improve the thermal stability, light stability, chemical stability, and dye affinity of the polyamide polymer. New stabilizer systems have also emerged which combine the unique properties of (I) in synergistic combinations with other additives. Examples can be found in EP 09 0 3 3 7 2 A1 or us 6; 0 6 3; 8 4 3. The compound (n or its derivative is also p "successfully stabilized the polyester resin, as can be seen in (E) [0096 7 A] (3) 200418796. The original general formula (I) Stabilizers are synthesized by combining difermented dichloride (jpc) with a three-dimensional limb-blocking formula of general formula (II), where the R] and R2 groups in formula (II) are as defined below. The middle system uses water as a bulking agent.

In order to achieve acceptable yields, it is necessary to use an excessive amount of amine component (II). The amine component of general formula (Π) is generally known to have poor biodegradability.

By. Since excess amine components must be washed out after reacting with water, a waste water that cannot be effectively treated in a conventional waste water plant is generated. The yields achievable by the above methods are limited due to the hydrolysis that occurs during the reaction stage. Therefore, due to the mentioned disadvantages, such a method known in the prior art cannot be transferred to a general manufacturing plant. [Summary of the Invention] -6-(4) (4) 200418796 are found that the use of certain combinations of organic solvents plus optimized combinations of pressure and temperature can result in a dramatic increase in overall yields over 10% and decrease The negative loading of organic matter in wastewater results in fewer environmental problems. Therefore, the purpose of the present invention is to propose a method for preparing a stabilizer of the general formula (!) By condensing isophthalocyanine dichloride (IPC) with a monoblock amine of general formula (II),

Wherein Ri is H, C6—Cyclocyclic or Ci—C4, and R2 is H, C i—C5—alkyl or C] —C; 〇—alkoxy, the method is characterized by the use of the entire procedure Organic solvents or their mixtures with water and the use of an optimized combination of pressure and temperature. Preferably, R! Is fluorene or C] -C2-alkyl and R2 is fluorene or C] -C2 alkyl, and the most preferred is methyl and R2 is fluorene. The reaction between IPC and component (II) is by stirring IPC to contain compound (Π), 30-70% by weight, preferably 40-60% by weight, and most preferably 50% by weight caustic soda solution in organic solvents. And water solution. A key step of the present invention is to use an organic solvent or a mixture of an organic solvent and -Ί (5) 200418796 water instead of using only water in the prior art. The organic aromatic hydrocarbon used is preferably xylene, or an aliphatic alcohol, and isopropyl alcohol is preferable. The best is the use of isopropanol or a mixture of isopropanol and water. The preferred ratio of isopropanol to water is 6 Q — 80 vol% isofluorene to 40 vol% water, and the best is 70 vol%. The yield of isopropanol and 300 can be improved from 85% to 96% of theory by using the mentioned solvents or the miscibility of these solvents with water; it means that they should be minimized. In addition, the use of excessive amounts of biotoxic amine components (which will reduce the yield. The IPC used in the present invention for amine penta (II) is, for example, 1 mole IPC to 1.80-2.00 mole (II), preferably 1.90 moles. Ear (II), the best is the ratio of 1 mole IPC to 1.85 mole. This can result in the smallest organic load in the wastewater, and the component (II) has obvious advantages in terms of biotoxicity. However, alone The solvent system of the present invention still cannot completely eliminate the problem of the method. Even if water and organic solvents are used under ambient pressure, (I) can only be separated to obtain small, viscous, cake-like particles to filter aggregates such as centrifuges or pumps. The air filter cannot be obtained. As a result, a large amount of water must be applied to effectively wash and receive the quality of the product. Therefore, another key of the present invention is the combination of reaction conditions such as force. This is another item. The advantage is that the filtration properties of the compound crystals can be significantly improved. The solvent is ethanol or a hydrate. Theta alcohol is 20 vol% hydrate, which will hydrolyze the inverse Π) instead of the mole ratio of 1.80-; ear (II ) As far as the previous skills mentioned Compound, which can be easily separated to reach the accessible temperature and pressure. Formula (I) -8- (6) (6) 200418796 IPC The addition of amine (II) in solvent / water / NaOH solution is 2 0 — 4 0 ° C, preferably 2 5 — 3 5 ° C, and the best at 30 ° C. After the addition of IPC is complete, the reaction mixture is stirred at the same temperature for 50 to 70 minutes, preferably 1 hour. The reaction mixture is then heated in a autoclave to a temperature of 90-110 ° C, preferably 10 (TC and at I 3 to 1.7 bars, preferably 1.5 bar system pressure). Under these conditions, the reaction product can be completely dissolved in the solvent and can easily separate the 2 * phases. The aqueous layer containing most of the salts, excess caustic and some isopropanol residues can be easily separated After the remaining solvent is distilled off, it can be processed in a traditional wastewater treatment plant in one step. After adding water, the organic layer is heated to a temperature of 130-140 ° C and a system of 3.0-4.0 bar is applied Pressure until all solids are dissolved. At this point the reaction mixture is cooled to ambient temperature and large crystals of the product of general formula (I) are formed, which can be separated using conventional filter combinations. By using the invention, the reaction yield can be obtained It can be increased to 96%, and the waste water consumption and load can be significantly reduced and the filtration properties of the formed reaction products can be optimized, which results in the largest product (I) product yield in a general manufacturing plant. So This invention is in ecological It has advantages. The method of the present invention produces a stabilizer of the general formula (I), which can also be used in stabilizer systems as shown in US 6,0 63; 8 4 3. In addition, other additives can be added according to different applications. Other additives are also contained in US 6,063; 843. (7) (7) 200418796 [Embodiments] The examples given are used to illustrate the advantages of the new method for preparing stabilizers of the general formula (I). Examples are those in which R is a dimethyl group and R2 = 中. In the formula (I), the stabilizer R is dimethyl and R2 = η is a commonly known strong stabilizer for polyamine polymers and is C Lari ant is sold under the trade name Nylostab ® s-EED (R). Example 1 In a 4-necked 2-liter flask equipped with a stirrer, dropping funnel, thermometer, and p (R) electrode, 150.5 g 2, 2 , 6,6-tetramethylpiperidine-4-yl monoamine (98.7%; 0.95 mole) and 85.2 g of a 50% NaOH solution (ι · 07 mole) were added to 47.0.0 g A mixture of liquid propanol and 2 6 0.0 g of demineralized water. 102.1 g of molten isophthalocyanine chloride (99.4%; 0.50 Mo) was added with stirring. ). During the process of putting in IP C, the temperature of the reaction mixture was maintained at 30 ° C by cooling with an ice bath. The reaction mixture was stirred for another 1 hour under the same conditions (temperature / ρΗ control). At this reaction stage A white suspension was formed in the reaction mixture. The reaction mixture was transferred to a 3-liter laboratory autoclave equipped with a stirrer and an internal temperature of -10- (8) 200418796 degrees and the mixture was heated to τ 1-1 0 0 ° C temperature. The resulting system pressure was about 1.5 bar and the solids were completely dissolved. Quantitative liquid phase formation: a lower aqueous phase containing salt and Na O Η aqueous solution and some isopropanol-an upper organic phase containing the desired product dissolved in isopropanol. The lower organic phase is removed under pressure and added to the reaction mixture 950.0 grams of demineralized water

The mixture was reheated to a temperature of 130 ° C and a corresponding system pressure of PI = about 3.3 bar until all solids were completely dissolved. The resulting suspension was cooled to a peripheral temperature of Ti ~ 30 ° C. The resulting white suspension was passed through a filter assembly equipped with a metal sieve, and the product was washed with 7 1 5.0 g of demineralized water to remove chloride ions and other impurities. The reaction product was placed in a vacuum oven and heated to constant weight. In the general formula (I), the yield of the reaction product of R] = methyl and r2 = Η is 200.0 g or 95.3% of theoretical 値 (the yield is based on a small amount of component tad).

Example 2 (comparative example) In a 4-necked 2-liter flask equipped with a stirrer, a dropping funnel, a thermometer and a pΗ electrode, 161.2 g of 2,2,6,6-tetramethylpiperidine 1 4 monoylamine (98.7%; 1.02 moles) and 93.8 grams of crushed ice cooled to a temperature of 7 ° C and added with stirring -11-200418796 ⑼ 1 〇2. 1 g of molten isophthalocyanine Chlorine (99. 4%; 0. 50 moles). During the charge of the IPC, the temperature of the reaction mixture was kept at 10 ° C. After adding IPC, use 4 5 0.0 g of demineralized water to dilute the viscous mass and add 133.3 g of a 30% NaOH solution (1.00 Mol). To the addition of Na 0 Η, add 3 00.0 g of demineralized water. To dilute the reaction mass. After stirring for 3 hours at 2 5 t, the viscous suspension was filtered on a laboratory suction filter and washed until the pH reached 10 (a total of 2400 grams of demineralized water was required). The filter cake was suspended in 600.0 grams of demineralized water, stirred for 30 minutes and filtered again on a laboratory suction filter to isolate and washed with 700.0 grams of demineralized water. The reaction product was heated to constant weight in a vacuum drying oven. The yield of the reaction product of R1 = methyl and r2 = h in the general formula (I) is 184.8 g or 83.6% of the theoretical 値 based on IPC. -12-(10) (10) 200418796 Table 1 Main results of new method) and comparative example 2 (old method) --- Example 1 Example 2 _ Amount (TAD *) g / batch ----- 150.5 161.2 Rhenium yield, grams;% -------- 200.0; 95.3 184.8; 83.6 filtrate 1 amount (g) " __ 524.0 4 3 8.6 COD * * mg / l 1 2000 4 5 000 TAD filtrate 1 ( G) 0.5 κ 1 amount of waste water (g) 32 8.5 23 63 COD * * mg / l 5200 5000 TAD (g) in wastewater 1 Ατττ πιτ 0.03 amount of filtrate 2 (g) Μ j \\\ 690 COD * * mg / Liter MW JWS 1900 TAD filtrate 2 (g) Μ j \\\ 0.002 Wastewater 2 amount (g) Μ j »\\ 2 800 0CD * * mg / liter 4E 1300 TAD in wastewater 2 (g) 4K λ \\\ ι f 11-* * TAD: 2,2,6,6—tetramethyl vein D fixed one 4 —one month female ** COD: chemical oxygen demand: oxidize the organic load in wastewater to the required oxygen As can be seen from Table 1, the amount of TAD / batch required for the reaction in Example 1 was significantly lower than in Example 2. Despite this, the -13- (11) 200418796 yield of the reaction product of formula ()) is still about 12% higher than that of Example 2. ° The amount of wastewater required and the amount of residual ATD in the wastewater are much larger than those in Example 2. Low, as can be seen from Table 1. Therefore, the novel method of the present invention is not only a progress in terms of favorable reaction conditions in Example 1, but also a progress in terms of waste water consumption and generated load. Example 3 The filtration properties of the reaction product (I) crystals of Examples 1 and 2 Rl dimethyl and R2 = rhenium were tested on a standard filtration unit. This unit is made of a steel pressure filter (1 = 0.5 m; d = 0.05 m; Co. BHS 'metal sieve 60 micron porosity). The filter unit was filled with a standard volume (800 ml) of the product suspension (I). The filter unit was closed and a pressure of 1 bar N 2 was applied. Filtration time is measured in relation to the volume of the filtrate produced during filtration. Good filtration time is associated with good filtration properties of the suspension: Table 2 (I) Filtration time (seconds) of the product suspension on a standard B Η I filter unit: filtrate 100 ml 200 ml 3 00 ml 400 ml Example 1 3 11 22 35 Example 2 40 175 370 470 As can be seen from Table 2, the filtration properties of the suspension of Example 1 were better than those of Examples 2 -14- (12) (12) 200418796 suspension The filtration properties are far better. Since this result is related to the filtering properties of the filter assembly for general manufacturing, a much higher capacity can be achieved using this novel manufacturing method.

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Claims (1)

200418796 (1) Scope of patent application 1. A method for preparing a stabilizer of the general formula (I) by condensing isophthalocyanine dichloride (IPC) with a sterically hindered amine of the general formula (II), IPC (II) (I) where R] is H, C6-cycloalkyl or C] -C4-alkyl, and 112 is H, Cl—C5—sinyl or Cl—Cio—sinoxy, the method of It is characterized by the use of an organic solvent or its mixture with water throughout the procedure and the use of an optimized combination of pressure V and temperature. 2. The method according to item 1 of the scope of patent application, wherein Ri is Η or Ci-C2-垸 group and 1 ^ 2 is ^ [or Cl-C2-courtyard base. 3. The method of claim 1 in which R! Is methyl and R2 is Η. 4. The method according to any one of claims 1 to 3, wherein the molar ratio of IPC to amine (II) is 1 to 1.8 to 2.0. 5. The method according to any one of claims 1 to 3, wherein the solvent is toluene, ethanol or isopropanol or a mixture of 60 to 80% by volume isopropyl alcohol and 20 to 40% by volume water . 6. The method according to any one of claims 1 to 3, wherein -16- (2) 200418796 is added at a temperature of 25 to 35 ° C; [PC is added to the solvent / water / NaOH Amine (11) in solution, and the reaction mixture was stirred at the same temperature for 50 to 70 minutes. 7. The method according to item 6 of the patent application, wherein the reaction mixture is then heated in a autoclave to a temperature of 90 to 110 ° C and a system pressure of 1.3 to 1.7 bar. 8 · The method according to item 7 of the patent application, wherein phase separation occurs and the organic phase is heated to a temperature of 130-140 ° C after addition of water and a system pressure of 3.0-4.0 bar. 9. The method according to item 8 of the patent application, wherein the compound of formula (I) is isolated after cooling to ambient temperature. -17- 200418796 (1) The designated representative drawing in this case is as follows: Figure _ (2), the component representative symbols of this representative drawing are simply explained: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: R Formula I